Aromatic polyesters and a method for producing the same

ABSTRACT

An aromatic polyester superior in heat resistance and mechanical properties and satisfactory in lightness and color tone is provided. The aromatic polyester has resorcinol structure, has the formula (1), ##STR1## wherein R is halogen, C 1  -C 5  alkyl, or phenyl; m is an integer of 0 to 2, and when m is 2, the two substituents represented by R may be different from each other; and gives a powder fraction having a lightness (L value) of 70 or more and a red degree (a value) of 5 or less, which powder fraction is obtained by pulverizing the heat-resistant aromatic polyester, sieving the pulverized polyester by Tyler standard sieves and being allowed to pass through 60-mesh sieve but not 325-mesh sieve.

TECHNICAL FIELD

The present invention relates to a heat-resistant aromatic polyester having a resorcinol structure which is superior in heat resistance, mechanical properties and melt-moldability and has very good lightness and color tone; and a method for producing the same.

BACKGROUND ART

The technologies in such fields as electric, electronic, office automation (OA), audio-visual (AV), and automotive industries have been making remarkable progress in recent years. Polymeric materials used in such new fields are required to have meritorious properties such as high strength and high heat resistance. They have come to be required to have high level properties such as high dimensional accuracy, strength, rigidity, solder heat resistance and thin-wall processability by the advancement of reduction of the size and wall thickness particularly of electric parts such as relay parts, coil bobbins and connectors. As one of the polymeric materials which can satisfy the requirements, aromatic polyesters are suitably used. Among the aromatic polyesters, particularly aromatic polyesters showing liquid crystalline property in molten state have desirable thin-wall processability and are rapidly coming into wide use as a material for electric parts.

However, the aromatic polyesters showing liquid crystalline property in molten state have such disadvantages as low impact resistance, low weld strength and high irregularity of shrinkage in every direction. Therefore, in fact, the improvement of these disadvantages has been strongly desired. Since these disadvantages are expected to be overcome by reducing the liquid crystalline property of the polyesters, the introduction of nucleus-substituted structure or a bending structure into the polymer chains, addition of glass fibers, etc. are now under investigation.

The aromatic polyesters showing liquid crystalline property in molten state have high heat resistance due to their stiff molecular chains. However, because of this, they have to be molded at elevated temperatures. Therefore, in some application fields wherein the reduction of heat resistance is accepted to some degree, there has been a strong requirement of developing an aromatic polyester showing liquid crystalline property in molten state which can be molded at relatively low temperatures. The introduction of a nucleus-substituted structure or a bending structure into the polymer chains has been likewise tried in order to lower the melting point of the polyesters without damaging their mechanical properties, thereby improving the moldability. When a notice is given to the introduction of a bending structure into the polymer chains, the use of resorcinol as a bending monomer is particularly of technical interest in view of its easy availability in industry.

Although acetylation method, phenyl esterification method and acid chloride method are known as the methods for producing aromatic polyesters, the aromatic polyesters showing liquid crystal property in molten state are mostly produced by acetylation method, in which polymerization is carried out by solution polymerization in a solvent having a high boiling point or by melt polymerization using substantially no solvent. In acetylation method, an aromatic hydroxy compound, one of the monomers, is converted into an acetic acid ester by the reaction between an aromatic hydroxy compound and acetic anhydride and the acetic acid ester is then polymerized by the intermolecular elimination of acetic acid. The conversion of an aromatic hydroxy compound into an acetic acid ester is generally conducted by adding acetic anhydride in an excess amount of about 1.1 moles per mole of the hydroxyl group and allowing the resulting mixture to react under reflux of acetic anhydride.

However, the preparation of resorcinol diacetate by the above method problematically accompanies the coloring of the reaction product and the formation of by-products. The purification of the colored reaction product by distillation under reduced pressure is still insufficient to obtain resorcinol diacetate having a high purity enough to use it as a monomer for the aromatic polyester. Thus, by the acetylation method, it was difficult to obtain a practically usable polymer having a resorcinol structure, sufficiently high molecular weight and good lightness and color tone, although such a polyester is expected to have desirable physical properties.

The use of the phenyl esterification method, in which polycondensation proceeds via intermolecular elimination of phenol, generally cannot raise the molecular weight of the resulting polymer so much. In addition, the size of the equipment for discharging the phenol generated during the elimination out of the system is obliged to be large due to the necessity of sufficiently keeping the temperature of the equipment at a certain level for avoiding the solidification of phenol which has such a high boiling point as 182° C. This method, therefore, is industrially unapplicable.

The acid chloride method, in which polycondensation proceeds via dehydrochlorination, generally cannot raise the molecular weight of the resulting polymer so much. In addition, the use of special corrosion-resisting material is required for constructing the equipment due to the corrosive property of hydrogen chloride gas generated during the reaction. This method, therefore, is industrially unapplicable.

DISCLOSURE OF THE INVENTION

The present inventors have extensively studied the acetylation of resorcinol. Particularly, conc. sulfuric acid remarkably accelerates this reaction, and the reaction exothermically proceeds in the presence of conc. sulfuric acid. However, the reaction product obtained is colored red. The polymer obtained by polymerizing the red-colored product has a low molecular weight and is intensely colored. Therefore, the polymer has no practical value. The present inventors analyzed this reaction product by high-performance liquid chromatography (HPLC) and unclear magnetic resonance (NMR) to find that the desired resorcinol diacetate had been formed in a yield of only about 90 mole %, and by-products such as resacetophenone formed by the replacement of hydrogen attached to the benzene nucleus by an acetyl group, etc. had been formed.

In order to solve the foregoing problems, the present inventors have extensively researched a catalyst which encourages the reaction between resorcinol and acetic anhydride so as to give resorcinol diacetate in high yields. As a result, surprisingly, the present inventors have found that tertiary amines represented by pyridine are a highly active catalyst for selectively preparing resorcinol diacetate, in other words, the presence of tertiary amines prevents the formation of by-products such as resacetophenone, etc.

That is, the present inventors have found a method for producing highly pure resorcinol diacetates characterized by carrying out the reaction between resorcinol and acetic anhydride in the presence of a tertiary amine in an amount of 0.01 part by weight or more, preferably 0.02 to 3 parts by weight, more preferably 0.03 to 2 parts by weight per 100 parts by weight of resorcinol.

The tertiary amines having highly selective catalytic activity include pyridine, triethylamine, N,N-dimethylaniline and 4-dimethylaminopyridine. Preferred ones having particularly superior selectivity include pyridine and 4-dimethylaminopyridine. Further, preferred ones which are low in the cost and easily usable in industry include pyridine, triethylamine and N,N-dimethylaniline. Particularly, pyridine is preferred.

The present inventors also have extensively studied on aromatic polyesters prepared using the highly pure resorcinol diacetate produced according to the present invention as one of the monomers. As a result, they have found that the use of the highly pure resorcinol diacetate gives a polymer having not only a sufficiently high molecular weight and a very good color tone but also superior heat resistance and mechanical properties and a good melt-moldability. The present inventors thus attained to the present invention.

The present invention relates to a heat-resistant aromatic polyester resin which has resorcinol structure, has the formula (1), ##STR2## wherein R is halogen, C₁ -C₅ alkyl, or phenyl; and m is an integer of 0 to 2, and when m is 2, the two substituents represented by R may be different from each other; and gives a powder fraction having a lightness (L value) of 70 or more and a red degree (a value) of 5 or less, which powder fraction is obtained by pulverizing the heat-resistant aromatic polyester to a particle size of 300 μm or less, sieving the pulverized polyester by Tyler standard sieves and being allowed to pass through 60-mesh sieve but not 325-mesh sieve; and a method for producing the aromatic polyester.

Particularly, in terms of the balance of physical properties, it is desirable for the aromatic polyester of the present invention to contain the repeating unit of the formula (1) and at least one repeating unit selected from the group consisting of the units contained in the formula groups (2), (3) and (4):

formula group (2), ##STR3## formula group (3), ##STR4## and formula group (4), ##STR5## wherein R is halogen, C₁ -C₅ alkyl or phenyl; X is either one of ##STR6## --O--, --CH₂ --, --CH₂ --CH₂ --, ##STR7## --SO₂ -- or --S--; and each of m and n is an integer of 0 to 2, and when the number of R in the repeating units is 2 or more, the two or more substituents represented by R may be different from each other.

Of these repeating units, preferred ones are those contained in the formula group (5),

formula group (5), ##STR8## wherein R, m and n are as defined above.

Of these, particularly preferred repeating units are those in which both m and n are zero, that is, those having no substituent R.

Selecting proper combinations out of these preferred repeating units permits the provision of a heat-resistant aromatic polyester having good physical properties and well-balanced characteristics between moldability and heat resistance.

The aromatic polyester composed of 40 to 80 mole % of the repeating unit of the formula (6), 29 mole % or less of the repeating unit of the formula (7), 1 to 30 mole % of the repeating unit of the formula (8) and 10 to 30 mole % of the repeating unit of the formula (9), is particularly preferred.

Also, the aromatic polyester composed of 40 to 80 mole % of the repeating unit of the formula (6), 1 to 30 mole % of the repeating unit of the formula (8) and 10 to 30 mole % of the repeating unit of the formula (9), is likewise preferred. ##STR9## wherein R is halogen, C₁ -C₅ alkyl or phenyl; and each of m and n is an integer of 0 to 2, and when the number of R in the repeating units is 2 or more, the two or more substituents represented by R may be different from each other.

Of these, particularly preferred repeating units are those in which both m and n are zero, that is, those having no substituent R.

Also, the aromatic polyester composed of 40 to 80 mole % of the repeating unit of the formula (10), 29 mole % or less of the repeating unit of the formula (11), 1 to 30 mole % of the repeating unit of the formula (12) and 10 to 30 mole % of the repeating unit of the formula (13), is particularly preferred:

Also, the aromatic polyester composed of 40 to 80 mole % of the repeating unit of the formula (10), 1 to 30 mole % of the repeating unit of the formula (12) and 10 to 30 mole % of the repeating unit of the formula (13), is likewise preferred. ##STR10## wherein R is halogen, C₁ -C₅ alkyl or phenyl; and m is an integer of 0 to 2, and when m is 2, the two substituents represented by R may be different from each other.

Of these repeating units, particularly preferred are those in which m is zero, that is, those having no substituent R.

The aromatic polyester having resorcinol structure [formula (1)] of the present invention is characterized not only by its high heat resistance, mechanical properties and melt-moldability but also by its good lightness and color tone. A method for measuring the lightness and color tone will be illustrated below.

An aromatic polyester resin is pulverized into a powder having a particle size of 300 μm or less. The powder is sieved by two kinds of Tyler standard sieve, one of which is a 60-mesh sieve (mesh size: 246 μm) and the other of which is a 325-mesh sieve (mesh size: 43 μm), to obtain a resin powder fraction ranging from a maximum particle size smaller than 246 μm to a minimum particle size of 43 μm or more. In order to indicate the object color of the powder thus obtained, its tristimulus values, X, Y and Z, were measured with a 1 colorimetric color-difference meter according to 0°-d method prescribed by JIS Z 8722. The lightness (L value) and red degree (a value) were obtained from these values with Hunter's color difference equation prescribed by JIS Z 8730. The larger the L value, the higher the lightness of the color, and the larger the a value, the intenser the reddish tone.

The aromatic polyester having resorcinol structure [formula (1)] of the present invention shows a lightness (L value) of 70 or more and a red degree (a value) of 5 or less when measured by the above method. The aromatic polyester having a lightness of 75 or more and a red degree of 3 or less have a high commodity value, so that they are preferred. Those having a lightness of 80 or more and a red degree of 2 or less are more preferred.

The present invention further relates to a method for producing a heat-resistant aromatic polyester which has resorcinol structure and has the formula (1) characterized by using as a monomer highly pure resorcinol diacetates produced by reacting a resorcinol having the formula (14), ##STR11## wherein R is halogen, C₁ -C₅ alkyl, or phenyl; and m is an integer of 0 to 2, and when m is 2, the two substituents represented by R may be different from each other, with acetic anhydride in the presence of a tertiary amine.

There are many examples of disclosure of the aromatic polyesters having resorcinol structure as described in JP-A-54-93095, JP-A-57-87423, JP-A-60-28428, JP-A-60-38426, JP-A-63-12629 and JP-A-63-317032; Japanese Patent Application No. 62-13979; JP-A-1-261416, JP-A-1-266131, JP-A-1-266132 and JP-A-2-51523; Polymer Journal, Vol. 21, pp. 615-622 (1989); and the like. None of the examples listed above teaches the use of a tertiary amine as an active catalyst for selectively producing monomer resorcinol diacetates, which use is described in the present invention. Additionally, they fail to contain detailed description on the purity of resorcinol diacetates.

Moreover, they contain no examples of disclosure at all that the liquid-crystal aromatic polyesters composed of the foregoing repeating units of the formulae (6), (7), (8) and (9) in the foregoing molar ratios, or the repeating units of the formulae (10), (11), (12) and (13) in the foregoing molar ratios have particularly superior mechanical properties and well-balanced characteristics between heat resistance and moldability.

Furthermore, many examples of disclosure state that resorcinol diacetates are pale yellow and transparent liquids at room temperature at normal pressure. However, the resorcinol diacetates produced by reacting a resorcinol with acetic anhydride in the presence of a tertiary amine are colorless and transparent liquids at room temperature at normal pressure.

The resorcinol diacetates produced by the above method have an extremely high purity, and give polymers having a sufficiently high molecular weight by the polymerization without causing any problems such as coloration, etc. The polymers, therefore, have high heat resistance and mechanical properties and a good melt-moldability.

The monomers from which the repeating units of the aromatic polyester disclosed in the present invention are derived are not critical provided that one of the monomers is a resorcinol diacetate produced in the presence of a tertiary amine. However, in view of the heat resistance of the resulting polymer, it is preferable to select an aromatic compound having one or more hydroxyl groups and/or one or more carboxyl groups in the molecule as the monomer other than the resorcinol diacetate.

Specifically, in terms of the balance of the physical properties, it is preferable to select as the other monomers at least one monomer giving a repeating unit selected from the group consisting of the repeating units contained in the group of the formulas (2), (3) and (4).

The proper selection of the repeating units imparts a liquid crystalline property in molten state to the aromatic polyester containing the repeating unit derived from the highly pure resorcinol diacetate. Specific examples of the repeating units giving the liquid-crystal aromatic polyester having good physical properties and well-balanced characteristics between heat resistance and moldability are those having the above-mentioned formulas (6), (7), (8) and (9), which may be combined within the above-mentioned molar ratios. The other specific examples of the repeating units are those having the above-mentioned formulas (10), (11), (12) and (13), which may be combined within the above-mentioned molar ratios. The desirable mechanical properties and well-balanced characteristics between heat resistance and moldability of the liquid-crystal aromatic polyester disclosed in the present invention are considered to be due to the bending structure formed by the introduction of the resorcinol structure into the molecular chain.

The aromatic polyester of the present invention is produced by solution polymerization with high-boiling solvents or by fusion polymerization with substantially no solvent according to the acetylation method using as starting materials aromatic diols including resorcinol. The acetate, a monomer, is obtained by reacting the corresponding hydroxy compound with acetic anhydride in the presence of a tertiary amine, as described above.

The polymerization may be carried out at normal pressure in an inert gas atmosphere or under reduced pressure. The molecular weight of the polymer can further be increased by pulverizing the obtained polymer and subjecting the pulverized polymer to solid-phase polymerization in which heat-treatment is carried out in an inert gas atmosphere or under reduced pressure.

Hereinafter, the methods for producing the aromatic polyester having resorcinol structure of the present invention will be illustrated in detail. Among the methods is also a method for producing the aromatic polyester using as a monomer the acetate of an aromatic hydroxy compound including resorcinol that has been synthesized in the presence of a tertiary amine. However, an illustration will be given here on a method of manufacture in which polymerization is carried out in situ after the synthesis of the acetate.

Generally, in order to obtain the polyester having a high molecular weight, it is necessary to equalize the numbers of moles of the hydroxyl group and carboxyl group. In the preparation of the aromatic polyester having resorcinol structure of the present invention, however, it is preferable to use a resorcinol in an amount fed larger than the stoichiometrically calculated amount, because the boiling point of resorcinol diacetate is lower than that of the acetate of other monomers. Specifically, it is preferable to feed the resorcinol in an amount 1 to 1.5 times, preferably 1 to 1.3 times as much as the stoichiometrically calculated one.

To a reactor are fed the monomers including resorcinol and acetic anhydride so that the molar amount of acetic anhydride is 1.1 times as much as the total number of mole of the hydroxyl groups of the monomers. After replacing air in the reactor by nitrogen, the mixture is well stirred to dissolve the monomers such as resorcinol, etc. in acetic anhydride. Thereafter, a tertiary amine is added thereto in an amount of 0.01 part by weight or more per 100 parts by weight of the aromatic hydroxy compound in the monomers. Thereafter, the contents of the reactor are heated, and acetylation is carried out for about 1 to about 3 hours at a reaction temperature (refluxing temperature) of about 80° to about 145° C. Subsequently, polymerization is carried out by raising the inner temperature of the reactor at a rate of 1° to 5° C./min while removing the formed acetic acid by distillation. The polymerization may be carried out at normal pressure in an inert gas atmosphere or under reduced pressure. The molecular weight of the polymer obtained can further be increased by pulverizing the polymer and subjecting the pulverized polymer to solid-phase polymerization in which heat-treatment is carried out in an inert gas atmosphere or under reduced pressure.

The aromatic polyester obtained by polymerizing proper species of monomers in a proper mixing ratio shows liquid crystalline property in molten state. At the time of fusion, the molecular chains of the polyester showing liquid crystalline property in molten state are hardly entangled with one another, so that the melt viscosity of the polyester is extremely low and the molecular chains are highly oriented in the flow direction by a slight shear force. Consequently, the molded products obtained from the polyester showing liquid crystalline property in molten state, although their anisotropy is large, have high strength, high stiffness and high heat resistance.

Various methods are available for determining the molecular weight of the aromatic polyester of the present invention and the physical properties which are a measure for knowing the molecular weight. Generally, the molecular weight of polymers which are insoluble in solvents cannot be determined directly by means such as light scattering method (LS), gel permeation chromatography (GPC), etc. It also cannot be evaluated by measuring the physical properties (e.g. solution viscosity) which are a measure for knowing the molecular weight. However, for polymers which are insoluble in solvents, the flow temperature defined below can be utilized as a measurable physical property item which is a measure for knowing the molecular weight.

Flow temperature: A temperature at which a polymer shows a melt viscosity of 48,000 poises when melted by heating at a rate of temperature-rise of 4° C./min and pushed out of a nozzle of 1 mm in internal diameter and 10 mm in length under a load of 100 kg/cm².

Also, for aromatic polyesters showing liquid crystalline property in molten state, the liquid crystallization temperature defined as a temperature at which the polymer shows optical anisotropy is also useful as a measure for knowing the molecular weight. The liquid crystallization temperature can be determined with a polarization microscope equipped with a heating stage. For polymers which are soluble in suitable solvents, the flow temperature and liquid crystallization temperature can be determined, and in addition, the analysis by LS and GPC also can be used.

The molecular weight of the aromatic polyester of the present invention is not critical. However, from the standpoints of heat resistance and mechanical characteristics, the flow temperature defined above is preferably 180° C. or more. From the standpoint of sufficient mechanical characteristics, a flow temperature of 200° C. or more is particularly preferred.

To the aromatic polyester of the present invention can be blended fillers used in conventional aromatic polyesters, if necessary. That is, fibrous reinforcing agents (e.g. glass fibers, silica-alumina fibers, wollastonite, carbon fibers, potassium titanate fibers), inorganic fillers (e.g. calcium carbonate, talc, mica, clay, glass beads), solid lubricants represented by polytetrafluoroethylene and graphite, antioxidants, heat stabilizers, etc. can be added thereto as need arises.

In pelletizing the aromatic polyester of the present invention, there is no particular limitation to means to blend the aromatic polyester and other components. That is, it is common practice to mix the aromatic polyester, fillers (e.g. glass fibers), pigments, heat stabilizers, etc. with a Henschel mixer, tumbler, etc., and melt-knead and pelletize the mixture through an extruder.

Originally, resorcinols are monomers having meta-orienting property and are of great interest in having such a property that the use thereof as a monomer for preparing highly crystalline aromatic polyesters efficiently reduces the melting point of the resulting polyesters and markedly improves the processability of the resulting polyesters.

However, in the absence of a catalyst, the reaction between resorcinols and acetic anhydride gave resorcinol diacetates of low purity. Therefore, it was impossible to produce aromatic polyesters having a resorcinol skeleton from the corresponding resorcinol diacetates by acetylation method, although good physical properties can be expected for such polyesters.

However, as shown in the disclosure of the present invention, resorcinol diacetates of high purity can be obtained by reacting resorcinols and acetic anhydride in the presence of a tertiary amine. Consequently, the polymerization using such highly pure resorcinol diacetates gives aromatic polyesters superior in heat resistance, mechanical properties, melt processability and color tone.

When the above aromatic polyester has liquid crystalline property in molten state, it is possible to provide a liquid-crystal aromatic polyester having will-balanced characteristics between heat resistance and moldability.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be illustrated with reference to the following examples, but it is not to be interpreted as being limited thereto. Physical properties in the examples were measured by the following methods.

(1) High-performance liquid chromatography (hereinafter referred to as HPLC): Measured with methanol/acetic acid (volume ratio: 1000/5) and water/acetic acid (volume ratio: 1000/5) as a mobile phase by means of the 600E Multisolvent Transportation System (mfd. by Waters, Millipore Corp.) according to the low-pressure gradient method. The column used was a octadecylsilyl (ODS) column of 6.0 mm in internal diameter and 15 cm in length. Calculation of determination was carried out by the absolute calibration method, and the conversion, selectivity and yield in every reaction were calculated from the values obtained.

(2) Proton nuclear magnetic resonance spectrometry (hereinafter referred to as ¹ H-NMR method): Measured at room temperature with tetramethylsilane as the standard of chemical shift by means of a Model AC-200P Proton Nuclear Magnetic Resonance Spectrometer (200, 133 MHz) (mfd. by Bulker Inc.). The sample solution was prepared by dissolving 10 mg of a sample in 0.4 ml of deutero dimethyl sulfoxide.

(3) Flow temperature: Measured using a Model CFT-500 Flow Tester (mfd. by Shimadzu Corp.). It is a temperature at which a polymer shows a melt viscosity of 48,000 poises when melted by heating at a rate of temperature-rise of 4° C./min and pushed out of a nozzle of 1 mm in internal diameter and 10 mm in length under a load of 100 kg/cm².

(4) Lightness (L value) and color tone [red degree (a value) and yellow degree (b value)]: The polymer was pulverized into particles having a particle size of 300 μm or less using a bantam mill (mfd. by Hosokawa Micron Inc.). Then, the particles were sieved with two Tyler standard sieves, one of which is a 60-mesh sieve (mesh size: 246 μm) and the other of which is a 325-mesh sieve (mesh size: 43 μm), to obtain a powder fraction ranging from a maximum particle size smaller than 246 μm to a minimum particle size of 43 μm or more.

In order to indicate the object color of the powdery sample thus obtained, its tristimulus values, X, Y and Z, were measured with a colorimetric color difference meter, Z-1001DP (mfd. by Nippon Denshoku Kogyo Inc.), according to the 0°-d form prescribed by JIS Z 8722, and the lightness (L value), red degree (a value) and yellow degree (b value) were obtained from the above values using Hunter's color difference equation prescribed in JIS Z 8730.

(5) Optical anisotropy: The optical anisotropy of the resin in molten state was examined by heating the powdery polymer on a heating state at a rate of temperature-rise of 10° C./min under polarized light and macroscopically observing the state of the polymer. When the resin did not melt perfectly as it was left still, the test was carried out under pressure by means of spring pressure.

(6) Gel permeation chromatography (GPC): HLC-8020 (produced by TOSOH CORP.) was used. The size of the column was 7.8 mm inside diameter and 30 cm length, and the mobile phase used was a mixed solution of 2,3,5,6-tetrafluorophenol (TFP) and chloroform (volume ratio: TFP/CHCl₃ =1/2.721). Five milligrams of the sample was dissolved in 5 ml of 2,3,5,6-tetrafluorophenol, and the resulting solution was diluted with chloroform to two times the volume. Thereafter, the solution was prefiltered through a filter having a pore size of 0.45 μm, and the filtrate was used for measurement. Calculation of the molecular weight was calculated using a calibration curve prepared with standard polystyrenes.

(7) Solution viscosity: Measured at 60° C. with tetrafluorophenol (TFP) as a solvent using a Ubbelohde's viscometer.

(8) Physical properties of molded product: The various physical properties of molded products were measured by the following methods.

Flexural strength and modulus of elasticity: Test pieces for bending (length: 127 mm, width: 12.7 mm, and thickness: 6.4 mm) were molded from the aromatic polyester of the present invention, and measurement was carried out according to ASTM D-790.

Izod impact strength without notch: Test pieces were prepared by cutting the test pieces for bending into two equal parts in the lengthwise direction, and measurement was carried out according to ASTM D-256.

Tensile strength of thin-wall molded product: The tensile strength was determined using dumb-bell test pieces for tensile test (wall thickness: 0.5 mm, length: 75 mm, and width of neck portion: 5 mm) molded from the aromatic polyester of the present invention. Due to the skin structure of the test pieces of the aromatic polyester having liquid crystalline property in molten state, the tensile strength depends largely upon the thickness of the test piece. Even when the molded product of the aromatic polyester has a thin wall, it shows high tensile strength.

Heat distortion temperature (HDT): Measured according to ASTM D-648 using the test piece for bending.

Solder heat resistance: Dumb-bell test pieces for tensile test (wall thickness: 1.2 mm, length: 75 mm, and width of neck portion: 5 mm) were molded from the aromatic polyester resin. The test pieces were immersed in a fusion bath of solder, HA60A, containing 60% of tin and 40% of lead. The temperature of the solder bath was raised by 5° C. while keeping the bath at every temperature for 60 seconds. The maximum temperature at which the test pieces showed no foaming nor deformation was determined and taken as the solder heat resistance. For example, when the test pieces first show foaming or deformation at 275° C., the solder heat resistance is determined to be 270° C.

Thin-wall flow length: Using a 4-piece mold of which each piece was rectangular (wall thickness: 0.3 mm, length: 46 mm, and width: 5 mm), the aromatic polyester in molten state was charged into the mold under prescribed injection conditions. And, the flow length in the lengthwise direction of every rectangle was measured, and the flow length was expressed in terms of the average value. Due to the low melt viscosity of the aromatic polyester having liquid crystalline property in molten state, the aromatic polyester shows large thin-wall flow length and good moldability.

REFERENTIAL EXAMPLES 1 TO 4 AND COMPARATIVE REFERENTIAL EXAMPLES 1 AND 2 Acetylation of Resorcinol--Catalytic Effect

In a 200-ml round-bottom flask equipped with a crescent stirring blade, a three-way stopcock and a Dimroth condenser were charged 0.5 mole (55.0 g) of resorcinol and 1.1 moles (112.2 g) of acetic anhydride. The atmosphere in the system was replaced by nitrogen by introducing nitrogen into the system through the three-way stopcock, and resorcinol was dissolved in acetic anhydride while rotating the crescent stirring blade at 120 rpm. Thereafter, 275 mg of pyridine (0.5 part by weight per 100 parts by weight of resorcinol), a tertiary amine, was added. The flask was immersed in an oil bath while streaming cooling water through the Dimroth condenser, and the oil bath was heated. Reaction was carried out for 1 hour while maintaining the inner temperature at 100° C. The reaction product obtained was a colorless and transparent liquid at room temperature (Referential Example 1).

Further, in the same manner as in Referential Example 1, three kinds of an acetic anhydride solution of resorcinol were prepared, and 275 mg each of triethylamine, N,N-dimethylaniline and 4-dimethylaminopyridine (0.5 part by weight per 100 parts by weight of resorcinol) was added thereto as a tertiary amine. In the same manner as in Referential Example 1, resorcinol was allowed to react with acetic anhydride. The reaction products obtained were all colorless and transparent liquids at room temperature (Referential Examples 2 to 4).

Next, an acetic anhydride solution of resorcinol prepared in the same manner as in Referential Example 1 was heated without adding a tertiary amine, and acetylation was carried out for 3 hours while refluxing acetic anhydride. The reaction product obtained was an orange and transparent liquid at room temperature (Comparative Referential Example 1).

One drop of conc. sulfuric acid was added to an acetic anhydride solution of resorcinol prepared in the same manner. As a result, the reaction system generated heat to raise the inner temperature to 102° C. Thereafter, the flask was immersed in an oil bath, and reaction was carried out for 1 hour while maintaining the inner temperature at 100° C. The reaction product obtained was a red and transparent liquid at room temperature (Comparative Referential Example 2).

The reaction products obtained in Comparative Referential Examples 1 and 2 and Referential Examples 1 to 4 were analyzed by HPLC, and the conversion, selectivity and yield on resorcinol diacetate and the percent formation of by-products were calculated. These results are collectively shown in Table 1.

Table 1 demonstrates that in Referential Example 1, the conversion, selectivity and yield are all 100%; in Referential Examples 2 to 4, the selectivity is 100%; and in all the Referential Examples 1-4, no by-products are produced. Also, the analysis of the reaction products obtained in Comparative Referential Examples 1 and 2 by NMR shows that most of the by-products are compounds having a resacetophenone structure produced by the replacement of the hydrogen atom attached to the benzene nucleus by an acetyl group.

COMPARATIVE REFERENTIAL EXAMPLE 3 Purification of Resorcinol Diacetate by Distillation Under Reduced Pressure

Purification of the reaction product obtained in Comparative Referential Example 1 by distillation under reduced pressure was tried. First, after removing acetic acid by distillation at normal pressure, the pressure in the system was reduced to 10 mmHg. Distillation under reduced pressure was then carried out at a kettle temperature of 165° C. and a vapor temperature of 155° C. The resorcinol diacetate thus obtained showed a purity of 98.6%. It reveals that it is impossible to prepare by distillation under reduced pressure resorcinol diacetate having a purity necessary to use it as a monomer for aromatic polyester.

EXAMPLES 1 TO 7 AND COMPARATIVE EXAMPLE 1 Aromatic Polyester (1) Having Resorcinol Structure

In a polymerization vessel equipped with an anchor-shaped stirring blade were charged p-hydroxybenzoic acid, tetraphthalic acid and resorcinol so that the total amount of these monomers was 12 moles and the molar ratio between them was varied as shown in Table 2. To the resulting mixture was added acetic anhydride in an amount of 1.1 moles per mole of hydroxyl groups. After stirring for 15 minutes, pyridine was added thereto in an amount of 0.5 part by weight per 100 parts by weight of resorcinol. Thereafter, the atmosphere in the reaction system was sufficiently replaced by nitrogen, and acetylation was carried out at a reaction temperature of 100° C. for 1 hour.

Thereafter, the contents of the vessel were heated to 270° C. at a rate of temperature-rise of 1° C./min while removing formed acetic acid by distillation. After maintaining the temperature at 270° C. for 90 minutes, the temperature was further raised to 300° C. at a rate of temperature-rise of 1° C./min.

Polymerization was then carried out for 50 minutes under a reduced pressure of 10 mmHg for Examples 1 to 3, and for 50 minutes at normal pressure for Examples 4 to 7. The polymers thus obtained were pulverized into particles of 300 μm or less in particle size by means of a Bantam mill (mfd. by Hosokawa Micron Inc.), and in Examples 4, 5 and 7, the particles were further subjected to solid-phase polymerization at 210° C. for 3 hours in nitrogen atmosphere.

Next, for comparison, an example (Comparative Example 1) will be shown in which an aromatic polyester having a resorcinol having a resorcinol skeleton was produced in the same composition as in Example 4 without using a catalyst such as pyridine, etc. Monomers in a molar ratio shown in Table 2 were charged in the same reactor as used in Example 4, and acetic anhydride was added thereto in an amount of 1.1 moles per mole of the hydroxyl group. Thereafter, the contents of the reactor were heated with stirring in nitrogen gas atmosphere, and acetylation reaction was carried out for 3 hours under reflux while maintaining the heater temperature at 180° C. Thereafter, polymerization at normal pressure and solid-phase polymerization were carried out in the same manner as in Example 4 to obtain a polymer.

Table 2 shows the results of analysis of the aromatic polyesters having a resorcinol structure obtained in Examples 1 to 7 and Comparative Example 1. Table 3 shows the physical properties of molded products of the aromatic polyesters obtained in Examples 4 to 6 and Comparative Example 1.

These results reveal that the aromatic polyesters having a resorcinol structure produced using a highly pure resorcinol diacetate synthesized in the presence of a tertiary amine are superior in heat resistance and mechanical properties and satisfactory in melt-moldability and color tone.

Further, it can be seen from Example 7 that the aromatic polyester having a higher molecular weight can be obtained by feeding resorcinol of 1.025 time as much as the equivalent weight.

EXAMPLES 8 TO 13 AND COMPARATIVE EXAMPLES 2 TO 7 Aromatic Polyester (2) Having a Resorcinol Structure

In a polymerization vessel equipped with an anchor-shaped stirring blade were charged p-hydroxybenzoic acid, terephthalic acid, resorcinol and an aromatic diol shown in Table 4 so that the total amount of these monomers was 12 moles and the molar ratio between them was varied as shown in Table 4. To the resulting mixture was added acetic anhydride in an amount of 1.1 moles per mole of hydroxyl groups. After stirring for 15 minutes, pyridine was added in an amount of 0.5 part by weight per 100 parts by weight of the total weight of resorcinol and the aromatic diol. Thereafter, the atmosphere in the reaction system was sufficiently replaced .by nitrogen, and acetylation was carried out for 1 hour at a reaction temperature of 100° C. Thereafter, the contents of the vessel were heated to 270° C. at a rate of temperature-rise of 1° C./min while removing formed acetic acid by distillation. After maintaining the temperature at 270° C. for 90 minutes, the temperature was further raised to 300° C. at a rate of temperature-rise of 1° C./min, and polymerization was carried out for 50 minutes under a reduced pressure of 10 mmHg (Examples 8 to 13).

Next, for comparison, examples (Comparative Examples 2 to 7) will be shown in which the aromatic polyesters having a resorcinol structure were produced using the same monomers and compositions as in Examples 8 to 13 without using a catalyst such as pyridine, etc. Monomers in a molar ratio shown in Table 4 were charged in the same reactor as used in Examples 8 to 13, and acetic anhydride was added thereto in an amount of 1.1 moles per mole of hydroxyl groups. Thereafter, the contents of the reactor were heated with stirring in a nitrogen gas atmosphere, and acetylation reaction was carried out for 3 hours under reflux while maintaining the heater temperature at 180° C. Thereafter, polymerization under reduced pressure was carried out in the same manner as in Examples 8 to 13 to obtain a polymer.

Table 4 shows the results of analysis of the aromatic polyesters having a resorcinol structure obtained in Examples 8 to 13 and Comparative Examples 2 to 7 and the physical properties of the molded products of the aromatic polyesters.

The results reveal that the aromatic polyesters having a resorcinol structure produced using a highly pure resorcinol diacetate synthesized in the presence of a tertiary amine are superior in heat resistance and mechanical characteristics and satisfactory in melt-moldability and color tone even if an aromatic diol other than resorcinol is used together as a monomer.

EXAMPLES 14 TO 26 AND COMPARATIVE EXAMPLE 8 Aromatic Polyester (3) Having Resorcinol Structure

In a polymerization vessel equipped with an anchor-shaped stirring blade were charged p-hydroxybenzoic acid, terephthalic acid, resorcinol and 4,4'-dihydroxydiphenyl so that the total amount of these monomers was 12 moles and the molar ratio between them was varied as shown in Table 5. To the resulting mixture was added acetic anhydride in an amount of 1.1 moles per mole of hydroxyl groups. After stirring for 15 minutes, pyridine was added in an amount of 0.5 part by weight per 100 parts by weight of the total weight of resorcinol and 4,4'-dihydroxydiphenyl.

Thereafter, the atmosphere in the reaction system was sufficiently replaced by nitrogen, and acetylation was carried out for 1 hour at a reaction temperature of 100° C. Thereafter, the contents of the vessel were heated to 270° C. at a rate of temperature-rise of 1° C./min while removing formed acetic acid by distillation. After maintaining the temperature at 270° C. for 1 hour, the temperature was further raised to 300° C. at a rate of temperature-rise of 1° C./min, and polymerization was carried out for 70 minutes at normal pressure. The reaction product in molten state was taken out of the system and solidified at room temperature. The yield in every case in Table 5 was in the range of 94 to 98% of the theoretical yield.

Every reaction product was pulverized into a powder of 300 μm or less in particle size using a Bantam mill (mfd. by Hosokawa Micron Inc.). The powder was further treated at 300° C. for 3 hours in a nitrogen gas atmosphere to obtain the powdery aromatic polyester of resorcinol structure having a flow temperature of 230° to 340° C. The lightness (L value) and color tone, a value and b value, of the aromatic polyester were measured according to the foregoing method. The results are collectively shown in Table 5. Table 5 demonstrates that the lightness and color tone are good in all the Examples.

In Examples 25 and 26, 100 parts by weight of the aromatic polyester and 67 parts by weight of a glass fiber (EFH75-01 produced by Central Glass Co. Ltd.) were mixed and melt-kneaded at a temperature of 240° to 360° C. on a twin-screw extruder (PCM-30 mfd. by Ikegai Iron Works, Ltd.) to produce a pellet having a flow temperature shown in Table 5. In examples other than Examples 25 and 26, pellets were produced in the same manner as above except that nothing was blended with the aromatic polyester.

First, the thin-wall flow length was measured by the foregoing method in which the pellets were injection-molded. And then, various test pieces were prepared by molding, and the physical properties were measured by the foregoing methods. The results are collectively shown in Table 6.

Comparing Comparative Example 8 with Examples 14 to 26, particularly with Examples 16 to 18, shows the following:

First, the improvement in tensile strength and thin-wall flow length of thin-wall molded products by the combined use of 4,4'-dihydroxydiphenyl and resorcinol, a meta-orienting monomer, as aromatic diols demonstrates that the liquid crystalline property of the aromatic polyester is not relieved but rather strengthened. However, the mechanical properties such as Izod impact strength are improved. In addition, the combined use of resorcinol with another aromatic diol strengthens the liquid crystalline property of the aromatic polyester. At the same time it eliminates the disadvantages, such as low impact strength, shared by conventional polyesters showing liquid crystalline property in molten state.

The beneficial nature of resorcinol that improves both the liquid crystalline property and mechanical properties of the aromatic polyester was a surprise also to the present inventors.

Moreover, when notice is given to the flow temperature, molding temperature and heat distortion temperature, its is shown that the combined use of resorcinol with another monomer aromatic diol lowers the flow temperature necessary for obtaining good physical properties and enables the molding at relatively low temperatures.

That is, since the use of resorcinol with another aromatic diol lowers the melting point of the polyester showing liquid crystalline property in molten state without damaging the mechanical properties thereof, it enables the provision of the polyester which can be molded at relatively low temperatures. Furthermore, it can be seen that the reinforcement of the polyester showing liquid crystalline property in molten state by a glass fiber raises the heat resistance to solder to 260° C. or more.

EXAMPLES 27 AND 31 AND COMPARATIVE EXAMPLE 9 Aromatic Polyester (4) Having Resorcinol Structure

In a polymerization vessel equipped with an anchor-shaped stirring blade were charged p-hydroxybenzoic acid, terephthalic acid, resorcinol and hydroquinone so that the total amount of these monomers was 12 moles and the molar ratio between them was varies as shown in Table 7. To the resulting mixture was added acetic anhydride in an amount of 1.1 moles per mole of hydroxyl groups. After stirring for 15 minutes, pyridine was added thereto in an amount of 0.5 part by weight per 100 parts by weight of the total weight of resorcinol and hydroquinone.

Thereafter, the atmosphere in the reaction system was sufficiently replaced by nitrogen, and acetylation was carried out for 1 hour at a reaction temperature of 100° C. Thereafter, the contents of the vessel were heated to 310° C. at a rate of temperature-rise of 1° C./min while removing formed acetic acid by distillation, and polymerization was carried out for 15 minutes at normal pressure.

The reaction product was taken out of the system and pulverized into a powder of 300 μm or less in particle size using a Bantam mill (mfd. by Hosokawa Micron Inc.). The powder was further treated at 300° C. for 3 hours in a nitrogen gas atmosphere to obtain the powdery aromatic polyester of resorcinol structure having a flow temperature of 290° to 350° C.

The lightness (L value) and color tone, a value and b value, of the aromatic polyester were measured according to the foregoing method. The results are collectively shown in Table 7. From Table 7, it can be seen that the lightness and color tone are good in all the Examples.

In Examples 27 and 31, 100 parts by weight of the aromatic polyester and 67 parts by weight of a glass fiber (EFH75-01 produced by Central Glass Co. Ltd.) were mixed and melt-kneaded at a temperature of 300° to 360° C. on a twin-screw extruder (PCM-30 produced by Ikegai Iron Works, Ltd.) to produce a pellet having a flow temperature shown in Table 7. In Examples other than Examples 27 and 31, pellets were produced in the same manner as above except that nothing was blended with the aromatic polyester. Various test pieces were prepared from the resulting pellets by injection molding, and the physical properties were measured by the foregoing methods. The results are collectively shown in Table 8.

Comparing Comparative Example 9 with Examples 27 to 31, particularly with Examples 28 to 29, shows the following:

The use of hydroquinone alone as a monomer aromatic diol (Comparative Example 9) gave an aromatic polyester which does not melt even when heated at the flow temperature or higher. Thus, no injection-moldable aromatic polyester can be obtained by the use of hydroquinone alone. In contrast, the combined use of hydroquinone and resorcinol, a meta-orienting monomer, as aromatic diols (Examples 27 to 31) gave an injection-moldable aromatic polyester. That is, it enables the provision of a polyester showing liquid crystalline property which has good mechanical properties and well-balanced characteristics between heat resistance and moldability.

REFERENCE EXAMPLES 5 TO 7 Acetylation of Resorcinol--Amount of Catalyst Added

Using the same reaction apparatus as used in Referential Example 1, three kinds of an acetic anhydride solution of resorcinol were prepared in the same manner as in Referential Example 1. Thereafter, pyridine was added as a tertiary amine to the above solutions in amounts of 0.05, 0.1 and 0.5 part by weight, respectively, per 100 parts by weight of resorcinol (Referential Examples 5 to 7). The flasks were immersed in an oil bath, and reaction was carried out under the conditions shown in Table 9. The reaction products were analyzed by HPLC, and the results are collectively shown in Table 9.

It can be seen that the addition of pyridine in an amount of 0.1 part by weight or more gave colorless and transparent resorcinol diacetate.

EXAMPLES 32 TO 34 Aromatic Polyester (5) Having Resorcinol Structure

In a polymerization vessel equipped with an anchor-shaped stirring blade were charged p-hydroxybenzoic acid, terephthalic acid and resorcinol so that the total amount of these monomers was 12 moles and the molar ratio between them was varied as shown in Table 10. To the resulting mixture was added acetic anhydride in an amount of 1.1 moles per mole of hydroxy groups. After stirring for 15 minutes, pyridine was added in an amount of 0.05 part by weight per 100 parts by weight of resorcinol. Thereafter, the atmosphere in the reaction system was sufficiently replaced by nitrogen, and acetylation was carried out for 1 hour under reflux.

Thereafter, the contents of the vessel were heated to 270° C. at a rate of temperature-rise of 1° C./min while removing formed acetic acid by distillation. After maintaining the temperature at 270° C. for 90 minutes, the temperature was further raised to 300° C. at a rate of temperature-rise of 1° C./min.

Thereafter, polymerization at normal pressure was carried out for 50 minutes. The polymers thus obtained were pulverized into particles of 300 μm or less in particle size using a Bantam mill (mfd. by Hosokawa Micron Inc.). In Examples 32 and 33, solid-phase polymerization was further carried out at 210° C. for 3 hours in nitrogen atmosphere.

The results of analysis of the aromatic polyesters obtained are shown in Table 10, and the physical properties of molded products are shown in Table 11.

From the above results, it can be seen that the aromatic polyesters having resorcinol structure produced using highly pure resorcinol diacetate synthesized in the presence of a tertiary amine are superior in heat resistance and mechanical properties and satisfactory in melt-moldability and color tone.

EXAMPLES 35 TO 44 Aromatic Polyester (6) Having Resorcinol Structure

In a polymerization vessel equipped with an anchor-shaped stirring blade were charged p-hydroxybenzoic acid, terephthalic acid, resorcinol and 4,4'-dihydroxydiphenyl so that the total amount of these monomers was 12 moles and the molar ratio between them was varied as shown in Table 12. To the resulting mixture was added acetic anhydride in an amount of 1.1 moles per mole of hydroxyl groups. After stirring for 15 minutes, pyridine was added in an amount of 0.05 part by weight per 100 parts by weight of the total weight of resorcinol and 4,4'-dihydroxydiphenyl.

Thereafter, the atmosphere in the reaction system was sufficiently replaced by nitrogen, and acetylation was carried out for 1 hour under reflux. Thereafter, the contents of the vessel were heated to 270° C. at a rate of temperature-rise of 1° C./min while removing formed acetic acid by distillation. After maintaining the temperature at 270° C. for 1 hour, the temperature was further raised to 300° C. at a rate of temperature-rise of 1° C./min, and polymerization was carried out for 70 minutes at normal pressure. The reaction product in molten state was taken out of the system and solidified at room temperature. The yield in every case in Table 12 was in the range of 94 to 98% of the theoretical yield.

Every reaction product was pulverized into a powder of 300 μm or less in particle size using a Bantam mill (mfd. by Hosokawa Micron Inc.). The powder was further treated at 300° C. for 3 hours in a nitrogen gas atmosphere to obtain a powdery aromatic polyester of resorcinol structure which has a flow temperature of 230° to 340° C. The lightness (L value) and color tone, a value and b value, of the aromatic polyester were measured according to the foregoing method. The results are collectively shown in Table 12. From Table 12, it can be seen that the lightness and color tone are good in all the Examples.

In Examples 43 and 44, 100 parts by weight of the aromatic polyester and 67 parts by weight of a glass fiber (EFH75-01 produced by Central Glass Co. Ltd.) were mixed and melt-kneaded at a temperature of 240° to 360° C. on a twin-screw extruder (PCM-30 produced by Ikegai Iron Works, Ltd.) to produce a pellet having a flow temperature shown in Table 12. In Examples other than Examples 43 and 44, pellets were produced in the same manner as above except that nothing was blended with the aromatic polyester.

First, the thin-wall flow length was measured by the foregoing method in which the pellets were injection-molded. And then, various test pieces were prepared by molding, and the physical properties were measured by the foregoing methods. The results are collectively shown in Table 13.

Since the use of resorcinol with another aromatic diol lowers the melting point of the polyester showing liquid crystalline property in molten state without damaging the mechanical properties thereof, it enables the provision of the polyester which can be molded at relatively low temperatures. Moreover, it can be seen that the reinforcement of the polyester showing liquid crystalline property in molten state with a glass fiber raises the heat resistance to solder to 260° C. or more.

EXAMPLES 45 AND 46 Aromatic Polyester (7) Having Resorcinol Structure

In a polymerization vessel equipped with an anchor-shaped stirring blade were charged p-hydroxybenzoic acid, terephthalic acid, resorcinol and hydroquinone so that the total amount of these monomers was 12 moles and the molar ratio between them was varied as shown in Table 14. To the resulting mixture was added acetic anhydride in an amount of 1.1 moles per mole of hydroxyl groups. After stirring for 15 minutes, pyridine was added in an amount of 0.05 part by weight per 100 parts by weight of the total weight of resorcinol and hydroquinone.

Thereafter, the atmosphere in the reaction system was sufficiently replaced by nitrogen, and acetylation was carried out for 1 hour under reflux. Thereafter, the contents of the vessel were heated to 310° C. at a rate of temperature-rise of 1° C./min while removing formed acetic acid by distillation, and polymerization was carried out for 15 minutes at normal pressure.

The reaction product was taken out of the system and pulverized into a powder of 300 μm or less in particle size using a Bantam mill (mfd. by Hosokawa Micron Inc.). The powder was further treated at 300° C. for 3 hours in a nitrogen gas atmosphere to obtain a powdery aromatic polyester having resorcinol structure of which the flow temperature is shown in Table 14.

The lightness (L value) and color tone, a value and b value, of the aromatic polyester were measured according to the foregoing method. The results are collectively shown in Table 14. Table 14 shows that the lightness and color tone are good in all the Examples.

100 Parts by weight of the aromatic polyester and 67 parts by weight of a glass fiber (EFH75-01 produced by Central Glass Co. Ltd.) were mixed and melt-kneaded at a temperature of 300° to 360° C. on a twin-screw extruder (PCM-30 produced by Ikegai Iron Works, Ltd.) to produce a pellet having a flow temperature shown in Table 14. Various test pieces were prepared from the resulting pellets by injection molding, and the physical properties were measured by the foregoing methods. The results are collectively shown in Table 15.

The combined use of resorcinol and hydroquinone enables the provision of a polyester showing liquid crystalline property in molten state which has good mechanical properties and well-balanced characteristics between heat resistance and moldability.

EXAMPLE 47

Even when m-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxy-l-naphthoic acid, methylhydroquinone, chlorohydroquinone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylethane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid and the like are used as a monomer copolymerized with resorcinol, an aromatic polyester having superior heat resistance and mechanical properties and good melt-moldability and color tone can be produced by using highly pure resorcinol diacetate synthesized in the presence of a tertiary amine.

                                      TABLE 1                                      __________________________________________________________________________                    Results of analysis by HPLC (mole %)                                                        Percent                                                           Conver-                                                                             Selec-  formation of                                              Catalyst                                                                               sion tivity                                                                             Yield                                                                              by-products                                                                           Coloration                                  __________________________________________________________________________     Comparative                                                                           --      100  90.0                                                                               90.0                                                                               9.8    Orange and                                  Referential                        transparent                                 Example 1                                                                      Comparative                                                                           Conc. sulfuric                                                                         100  93.1                                                                               93.1                                                                               6.6    Red and                                     Referential                                                                           acid                        transparent                                 Example 2 -Referential                                                                Pyridine                                                                               100  100 100 0      Colorless and                               Example 1                          transparent                                 Referential                                                                           Triethylamine                                                                          82.6 100 82.6                                                                               0      Colorless and                               Example 2                          transparent                                 Referential                                                                           N,N-dimethyl-                                                                          78.4 100 78.4                                                                               0      Colorless and                               Example 3                                                                             aniline                     transparent                                 Referential                                                                           4-Dimethyl-                                                                            100  100 100 0      Colorless and                               Example 4                                                                             aminopyridine               transparent                                 __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________                                GPC                                                                            Number                                                                               Weight                                               Molar ratio of monomers                                                                       Flow average                                                                              average                                              p-Hydroxy                                                                            Tere-    temper-                                                                             molecular                                                                            molecular  Lightness and                                                                          Liquid crystalline                benzoic                                                                              phthalic                                                                            Resor-                                                                             ature                                                                               weight                                                                               weight     color tone                                                                             property in molten                acid  acid cinol                                                                              (°C.)                                                                        (M.sub.n)                                                                            (M.sub.W)                                                                            M.sub.W /M.sub.n                                                                    L a  b  state                      __________________________________________________________________________     Example 1                                                                              0    100  100 262  1.43 × 10.sup.4                                                                3.39 × 10.sup.4                                                                2.37 83                                                                               1.1                                                                               19.8                                                                              Not observed               Example 2                                                                             100   100  100 231  1.18 × 10.sup.4                                                                3.01 × 10.sup.4                                                                2.55 83                                                                               1.0                                                                               19.8                                                                              Not observed               Example 3                                                                             200   100  100 244  1.55 × 10.sup.4                                                                4.77 × 10.sup.4                                                                3.08 84                                                                               0.9                                                                               19.8                                                                              Not observed               Example 4                                                                             350   100  100 259  1.87 × 10.sup.4                                                                5.30 × 10.sup.4                                                                2.84 85                                                                               0.9                                                                               19.7                                                                              Observed                   Example 5                                                                             450   100  100 261  9.44 × 10.sup.3                                                                2.71 × 10.sup.4                                                                2.87 87                                                                               0.9                                                                               19.7                                                                              Observed                   Example 6                                                                             800   100  100 309  Insoluble in solvents                                                                           88                                                                               0.9                                                                               19.7                                                                              Observed                   Example 7                                                                             350   100    102.5                                                                            276  2.00 × 10.sup.4                                                                6.67 × 10.sup.4                                                                3.34 84                                                                               0.9                                                                               19.8                                                                              Observed                   Comparative                                                                           350   100  100 223  9.98 × 10.sup.3                                                                2.50 × 10.sup.4                                                                2.51 61                                                                               7.6                                                                               22.6                                                                              Immeasurable owing         Example 1                                           to violent                                                                     coloration                 __________________________________________________________________________

                  TABLE 3                                                          ______________________________________                                                 Molding                                                                        Temper-         Flexural  Flexural                                             ature  HDT      strength  modulus                                              (°C.)                                                                          (°C.)                                                                            (Kgf/cm.sup.2)                                                                           (kgf/cm.sup.2)                               ______________________________________                                         Example 4 300      166      1060    32200                                      Example 5 300      167      790     38000                                      Example 6 370      207      700     72000                                      Comparative                                                                              300      151      660     29900                                      Example 1                                                                      ______________________________________                                    

                                      TABLE 4                                      __________________________________________________________________________            Molar ratio of monomers                                                        p-Hydroxy-                                                                           Tere-                                                                    benzoic                                                                              phthalic                                                                            Resor-                                                                             Aromatic                                                        acid  acid cinol                                                                              diol (species)                                           __________________________________________________________________________     Example 8                                                                             400   100  90  10   (hydroquinone)                                      Example 9                                                                             400   100  50  50   (phenylhydroquinone)                                Example 10                                                                            400   100  60  40   (4,4'-dihydroxydiphenyl)                            Example 11                                                                            400   100  50  50   [2,2-bis(4-hydroxyphenyl)propane]                   Example 12                                                                            400   100  50  50   (2,6-dihydroxynaphthalene)                          Example 13                                                                            400   100  50  50   (1,4-dihydroxynaphthalene)                          Comparative                                                                           400   100  90  10   (hydroquinone)                                      Example 2                                                                      Comparative                                                                           400   100  50  50   (phenylhydroquinone)                                Example 3                                                                      Comparative                                                                           400   100  60  40   (4,4'-dihydroxydiphenyl)                            Example 4                                                                      Comparative                                                                           400   100  50  50   [2,2-bis(4-hydroxyphenyl)propane]                   Example 5                                                                      Comparative                                                                           400   100  50  50   (2,6-dihydroxynaphthalene)                          Example 6                                                                      Comparative                                                                           400   100  50  50   (1,4-dihydroxynaphthalene)                          Example 7                                                                      __________________________________________________________________________            Flow   Liquid crystalline                                                                         Lightness and                                                                         Molding                                              temperature                                                                           property in molten                                                                         color tone                                                                            temperature                                                                           HDT                                           (°C.)                                                                          state       L a b  (°C.)                                                                          (°C.)                           __________________________________________________________________________     Example 8                                                                             309    Observed    86                                                                               0.9                                                                              19.8                                                                              360    144                                    Example 9                                                                             286    Observed    87                                                                               0.9                                                                              19.7                                                                              320    132                                    Example 10                                                                            280    Observed    85                                                                               1.0                                                                              19.9                                                                              310    196                                    Example 11                                                                            297    Not observed                                                                               86                                                                               0.9                                                                              19.8                                                                              330    121                                    Example 12                                                                            273    Observed    84                                                                               1.1                                                                              20.0                                                                              310    109                                    Example 13                                                                            284    Observed    84                                                                               1.2                                                                              19.8                                                                              310    111                                    Comparative                                                                           254    Immeasurable owing to                                                                      61                                                                               6.6                                                                              21.5                                                                              360    122                                    Example 2     violent coloration                                               Comparative                                                                           266    Immeasurable owing to                                                                      60                                                                               8.0                                                                              22.7                                                                              320    112                                    Example 3     violent coloration                                               Comparative                                                                           260    Immeasurable owing to                                                                      59                                                                               8.0                                                                              23.1                                                                              310    172                                    Example 4     violent coloration                                               Comparative                                                                           272    Immeasurable owing to                                                                      59                                                                               7.2                                                                              23.0                                                                              330    112                                    Example 5     violent coloration                                               Comparative                                                                           250    Immeasurable owing to                                                                      57                                                                               8.1                                                                              23.2                                                                              310    102                                    Example 6     violent coloration                                               Comparative                                                                           262    Immeasurable owing to                                                                      58                                                                               8.0                                                                              23.7                                                                              310    100                                    Example 7     violent coloration                                               __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________                                 Glass                                                     Molar ratio of monomers                                                                             fiber       Flow Molding                                  p-Hydroxy                                                                            Tere-    4,4'- (part                                                                               Lightness and                                                                         temper-                                                                             temper-                                  benzoic                                                                              phthalic                                                                            Resor-                                                                             dihydroxy-                                                                           by   color tone                                                                            ature                                                                               ature                                    acid  acid cinol                                                                              diphenyl                                                                             weight)                                                                             L a b  (°C.)                                                                        (°C.)                      __________________________________________________________________________     Example 14                                                                            150   100  50  50    --   80                                                                               1.9                                                                              19.9                                                                              275  305                               Example 15                                                                            250   100  50  50    --   83                                                                               1.8                                                                              19.8                                                                              280  305                               Example 16                                                                            300   100  25  75    --   86                                                                               0.7                                                                              19.1                                                                              306  335                               Example 17                                                                            300   100  50  50    --   84                                                                               1.6                                                                              19.8                                                                              276  305                               Example 18                                                                            300   100  75  25    --   83                                                                               1.9                                                                              19.8                                                                              217  245                               Example 19                                                                            350   100  50  50    --   85                                                                               1.0                                                                              19.8                                                                              287  320                               Example 20                                                                            375   100  50  50    --   86                                                                               1.0                                                                              19.7                                                                              285  310                               Example 21                                                                            400   100  50  50    --   85                                                                               0.9                                                                              19.8                                                                              293  315                               Example 22                                                                            450   100  50  50    --   86                                                                               0.8                                                                              19.7                                                                              296  325                               Example 23                                                                            500   100  50  50    --   87                                                                               0.9                                                                              19.7                                                                              300  325                               Example 24                                                                            700   100  50  50    --   87                                                                               0.8                                                                              19.6                                                                              300  325                               Example 25                                                                            350   100  50  50    67   85                                                                               0.9                                                                              19.9                                                                              297  330                               Example 26                                                                            400   100  50  50    67   86                                                                               0.9                                                                              19.9                                                                              303  330                               Comparative                                                                           300   100   0  100   --   Not measured                                                                          326  340                               Example 8                                                                      __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________            Mechanical properties Thermal properties                                                        Tensile                                                                             Heat dis-                                                                 strength                                                                            tortion   Moldability                                                     of thin-                                                                            temper-                                                                             Heat Thin-wall                                                Izod   wall ature                                                                               resist-                                                                             flow length                                    Flexural                                                                            Flexural                                                                            impact molded                                                                              (18.6                                                                               ance to                                                                             (measurement                                   strength                                                                            modulus                                                                             strength                                                                              product                                                                             kg/cm.sup.2)                                                                        solder                                                                              temperature)                                   (kg/cm.sup.2)                                                                       (kg/cm.sup.2)                                                                       (kg · cm/cm)                                                                 (kg/cm.sup.2)                                                                       (°C.)                                                                        (°C.)                                                                        (mm)                                    __________________________________________________________________________     Example 14                                                                            1,460                                                                               111,000                                                                             29     2,310                                                                               109  Not  25.0(320° C.)                                                      measured                                     Example 15                                                                            1,560                                                                               115,100                                                                             26     2,450                                                                               128  Not  24.7(320° C.)                                                      measured                                     Example 16                                                                            1,500                                                                               133,000                                                                             80     3,370                                                                               254  Not  Not measured                                                              measured                                     Example 17                                                                            1,120                                                                                63,500                                                                             28     3,080                                                                               155  Not  25.5(320° C.)                                                      measured                                     Example 18                                                                            1,110                                                                                63,300                                                                             26     2,010                                                                               110  Not  Not measured                                                              measured                                     Example 19                                                                            1,470                                                                                93,600                                                                             37     3,470                                                                               187  Not  24.8(330° C.)                                                      measured                                     Example 20                                                                            1,590                                                                               132,100                                                                             35     2,160                                                                               213  Not  23.2(330° C.)                                                      measured                                     Example 21                                                                            1,670                                                                               122,400                                                                             30     2,460                                                                               231  Not  20.8(330° C.)                                                      measured                                     Example 22                                                                            1,260                                                                               122,700                                                                             20     1,630                                                                               247  Not  21.2(340° C.)                                                      measured                                     Example 23                                                                            1,250                                                                               110,990                                                                             20     2,100                                                                               250  Not  19.9(340° C.)                                                      measured                                     Example 24                                                                            1,230                                                                               100,750                                                                             22     1,960                                                                               249  Not  19.8(340° C.)                                                      measured                                     Example 25                                                                            1,560                                                                               132,800                                                                             27     2,150                                                                               204  260  22.3(340° C.)                    Example 26                                                                            1,760                                                                               165,100                                                                             30     1,910                                                                               228  270  19.3(340° C.)                    Comparative                                                                             600                                                                                49,700                                                                              5       930                                                                               281  Not   9.7(320° C.)                    Example 8                         measured                                     __________________________________________________________________________

                                      TABLE 7                                      __________________________________________________________________________                                Glass            Mold-                                     Molar ratio of monomers                                                                            fiber       Flow ing                                       p-Hydroxy                                                                            Tere-         (part                                                                               Lightness and                                                                         temper-                                                                             temper-                                   benzoic                                                                              phthalic                                                                            Resor-                                                                             Hydro-                                                                              by   color tone                                                                            ature                                                                               ature                                     acid  acid cinol                                                                              quinone                                                                             weight)                                                                             L a b  (°C.)                                                                        (°C.)                       __________________________________________________________________________     Example 27                                                                            300   100  75  25   67   87                                                                               0.8                                                                              19.8                                                                              298  340                                Example 28                                                                            350   100  70  30   --   87                                                                               0.7                                                                              19.7                                                                              305  340                                Example 29                                                                            350   100  90  10   --   85                                                                               0.9                                                                              19.9                                                                              280  320                                Example 30                                                                            400   100  70  30   --   87                                                                               0.7                                                                              19.6                                                                              343  380                                Example 31                                                                            400   100  70  30   67   87                                                                               0.8                                                                              19.6                                                                              330  370                                Comparative                                                                           350   100   0  100  --   Not    300  Not                                Example 9                       measured    moldable                           __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________             Mechanical properties                                                                              Tensile  Thermal property                                              Izod    strength of                                                                             Heat distortion                                   Flexural                                                                             Flexural                                                                             impact  thin-wall                                                                               temperature                                       strength                                                                             modulus                                                                              strength                                                                               molded product                                                                          (18.6 kg/cm.sup.2)                                (kg/cm.sup.2)                                                                        (kg/cm.sup.2)                                                                        (kg · cm/cm)                                                                  (kg/cm.sup.2)                                                                           (°C.)                              __________________________________________________________________________     Example 27                                                                             1,300 100,000                                                                              16      1,320    133                                       Example 28                                                                             1,000  58,000                                                                              17      1,310    137                                       Example 29                                                                             1,200  48,100                                                                              33      1,850    120                                       Example 30                                                                             1,000  88,000                                                                              26      2,650    186                                       Example 31                                                                             1,500 145,000                                                                              15      1,400    203                                       Comparative                                                                            Molded products cannot be obtained.                                                                         Not moldable                              Example 9                                                                      __________________________________________________________________________

                                      TABLE 9                                      __________________________________________________________________________                             Reaction conditions                                                                           Results of                              Resorcinol     Pyridine            Time                                                                               analysis by HPLC (mole %)               (part by weight)                                                                              (part by weight)                                                                        Temperature (°C.)                                                                  (min)                                                                              Conversion                                                                           Selectivity                                                                          Yield                                                                              Coloration              __________________________________________________________________________     Referential                                                                          100      0.05     Refluxing temperature                                                                     60  100   100   100 Pale yellow             Example 5                                              and transparent         Referential                                                                          100      0.1      "          60  100   100   100 Colorless               Example 6                                              and transparent         Referential                                                                          100      0.5      "          60  100   100   100 Colorless               Example 7                                              and                     __________________________________________________________________________                                                            transparent        

                                      TABLE 10                                     __________________________________________________________________________                               GPC                                                  Molar ratio of monomers                                                                             Flow Number ave-                                                                           Weight avera-                                 p-Hydroxy-  Tere-    temper-                                                                             rage molecu-                                                                          ge molecular                                                                               Lightness and                                                                         Liquid crystalline         benzoic     phthalic                                                                            Resor-                                                                             ature                                                                               lar weight                                                                            weight      color tone                                                                            property in molten         acid        acid cinol                                                                              (°C.)                                                                        (M.sub.n)                                                                             (M.sub.w)                                                                              M.sub.w /M.sub.n                                                                   L a b  state                      __________________________________________________________________________     Example 32                                                                           350   100  100 261  1.90 × 10.sup.4                                                                 5.51 × 10.sup.4                                                                  2.90                                                                               83                                                                               1.0                                                                              19.7                                                                              Observed                   Example 33                                                                           450   100  100 260  9.03 × 10.sup.3                                                                 2.66 × 10.sup.4                                                                  2.95                                                                               86                                                                               0.9                                                                              19.7                                                                              Observed                   Example 34                                                                           800   100  100 310  Insoluble in solvents                                                                             86                                                                               0.9                                                                              19.7                                                                              Observed                   __________________________________________________________________________

                  TABLE 11                                                         ______________________________________                                         Molding                 Flexural  Flexural                                     temperature    HDT      strength  modulus                                      (°C.)   (°C.)                                                                            (kgf/cm.sup.2)                                                                           (kgf/cm.sup.2)                               ______________________________________                                         Example 32                                                                             300        165      1040    32200                                      Example 33                                                                             300        168       780    38100                                      Example 34                                                                             370        207       720    73000                                      ______________________________________                                    

                                      TABLE 12                                     __________________________________________________________________________            Molar ratio of monomers                                                        p-Hydroxy-                                                                            Tere-     4,4'-          Lightness and                                                                          Flow    Molding                        benzoic                                                                               phthalic                                                                            Resor-                                                                              dihydroxy-                                                                           Glass fiber                                                                             color tone                                                                             temperature                                                                            temperature                    acid   acid cinol                                                                               diphenyl                                                                             (part by weight)                                                                        L a  b  (°C.)                                                                           (°C.)            __________________________________________________________________________     Example 35                                                                            250    100  50   50    --       83                                                                               1.9                                                                               19.8                                                                              279     305                     Example 36                                                                            300    100  25   75    --       85                                                                               0.7                                                                               19.1                                                                              305     335                     Example 37                                                                            300    100  50   50    --       84                                                                               1.6                                                                               19.7                                                                              277     305                     Example 38                                                                            300    100  75   25    --       82                                                                               1.9                                                                               19.8                                                                              217     245                     Example 39                                                                            350    100  50   50    --       84                                                                               1.0                                                                               19.8                                                                              288     320                     Example 40                                                                            375    100  50   50    --       86                                                                               1.1                                                                               19.7                                                                              284     310                     Example 41                                                                            400    100  50   50    --       84                                                                               0.9                                                                               19.8                                                                              295     315                     Example 42                                                                            450    100  50   50    --       86                                                                               0.8                                                                               19.7                                                                              296     325                     Example 43                                                                            350    100  50   50    67       84                                                                               0.9                                                                               19.9                                                                              296     330                     Example 44                                                                            400    100  50   50    67       85                                                                               0.9                                                                               19.9                                                                              305     330                     __________________________________________________________________________

                                      TABLE 13                                     __________________________________________________________________________                                                           Moldability                     Mechanical properties        Thermal properties                                                                               Thin-wall                                           Tensile strength                                                                        Heat distortion   flow length                     Flexural                                                                             Flexural                                                                             Izod impact                                                                            of thin-wall                                                                            temperature                                                                             Heat resistance                                                                         (measurement                    strength                                                                             modulus                                                                              strength                                                                               molded product                                                                          (18.6 kg/cm.sup.2)                                                                      to solder                                                                               temperature)                    (kg/cm.sup.2)                                                                        (kg/cm.sup.2)                                                                        (kg · cm/cm)                                                                  (kg/cm.sup.2)                                                                           (°C.)                                                                            (°C.)                                                                            (mm)                     __________________________________________________________________________     Example 35                                                                            1,550 115,000                                                                              25      2,450    128      Not measured                                                                            24.9 (320°                                                              C.)                      Example 36                                                                            1,480 132,900                                                                              75      3,370    254      Not measured                                                                            Not measured             Example 37                                                                            1,130  63,500                                                                              28      3,080    155      Not measured                                                                            25.5 (320°                                                              C.)                      Example 38                                                                            1,120  63,200                                                                              26      2,010    110      Not measured                                                                            Not measured             Example 39                                                                            1,480  93,800                                                                              40      3,490    188      Not measured                                                                            24.5 (330°                                                              C.)                      Example 40                                                                            1,590 132,100                                                                              35      2,160    213      Not measured                                                                            23.2 (330°                                                              C.)                      Example 41                                                                            1,670 122,600                                                                              35      2,460    232      Not measured                                                                            20.6 (330°                                                              C.)                      Example 42                                                                            1,250 122,700                                                                              20      1,630    247      Not measured                                                                            21.2 (340°                                                              C.)                      Example 43                                                                            1,540 133,000                                                                              27      2,170    205      260      22.0 (340°                                                              C.)                      Example 44                                                                            1,770 165,300                                                                              35      1,930    228      270      19.3 (340°                                                              C.)                      __________________________________________________________________________

                                      TABLE 14                                     __________________________________________________________________________            Molar ratio of monomers                                                        P-Hydroxy-                                                                            Tere-                    Lightness and                                                                          Flow    Molding                        benzoic                                                                               phthalic                                                                            Resor-                                                                              Hydro-                                                                               Glass fiber                                                                             color tone                                                                             temperature                                                                            temperature                    acid   acid cinol                                                                               quinone                                                                              (part by weight)                                                                        L a  b  (°C.)                                                                           (°C.)            __________________________________________________________________________     Example 45                                                                            300    100  75   25    67       85                                                                               0.9                                                                               19.8                                                                              300     340                     Example 46                                                                            400    100  70   30    67       85                                                                               0.9                                                                               19.6                                                                              330     370                     __________________________________________________________________________

                                      TABLE 15                                     __________________________________________________________________________            Mechanical properties        Thermal property                                                      Tensile strength                                                                        Heat distortion                                   Flexural                                                                             Flexural                                                                             Izod impact                                                                            of thin-wall                                                                            temperature                                       strength                                                                             modulus                                                                              strength                                                                               molded product                                                                          (18.6 kg/cm.sup.2)                                (kg/cm.sup.2)                                                                        (kg/cm.sup.2)                                                                        (kg · cm/cm)                                                                  (kg/cm.sup.2)                                                                           (°C.)                               __________________________________________________________________________     Example 45                                                                            1,400 100,200                                                                              19      1,350    135                                        Example 46                                                                            1,400 145,000                                                                              15      1,410    203                                        __________________________________________________________________________

INDUSTRIAL APPLICABILITY

The use of highly pure, meta-orienting resorcinol diacetates obtained by acetylating a resorcinol having the formula (14) in the presence of a tertiary amine enables the synthesis of an aromatic polyestr having a good balance between heat resistance, mechanical properties and melt-moldability and having a very good color tone, of which the industrial value is very high. 

We claim:
 1. A heat-resistant aromatic polyester resin which has resorcinol structure, has the formula (1), ##STR12## and gives a powder fraction having a lightness (L value) of 80 or more and a red degree (a value) of 3 or less, which powder fraction is obtained by pulverizing the heat-resistant aromatic polyester, sieving the pulverized polyester by Tyler standard sieves and being allowed to pass through 60-mesh sieve but not 325-mesh sieve, which heat-resistant aromatic polyester resin is produced by a method which comprises polymerizing a monomer of a resorcinol diacetate produced by reacting a resorcinol having the formula (14), ##STR13## with acetic anhydride in the presence of a tertiary amine in an amount of 0.02 to 3 parts by weight per 100 parts by weight of resorcinol.
 2. A heat-resistant aromatic polyester according to claim 1 characterized by containing at least one repeating unit selected from the group consisting of the units contained in the formula groups (2), (3) and (4),formula group (2), ##STR14## formula group (3), ##STR15## and formula group (4), ##STR16## wherein R is halogen, C₁ -C₅ alkyl, or phenyl; X is either one of ##STR17## --O--, --CH₂ --, --CH₂ --CH₂ --, ##STR18## --SO₂ -- or --S--; and m is an integer of 0 to 2, and when the number of R in the repeating units is 2 or more, the two or more substituents represented by R may be different from each other.
 3. A heat-resistant aromatic polyester according to claim 1 characterized by comprising 40 to 80 mole % of the repeating unit of the formula (6), 29 mole % or less of the repeating unit of formula (7), 1 to 30 mole % of the repeating unit of formula (8) and 10 to mole % of the repeating unit of the formula (9), ##STR19##
 4. A heat-resistant aromatic polyester according to claim 1 characterized by comprising 40 to 80 mole % of the repeating unit of the formula (6), 1 to 30 mole % of the repeating unit of the formula (8) and 10 to 30 mole % of t he repeating unit of the formula (9), ##STR20##
 5. A heat-resistant aromatic polyester according to claim 1 characterized by comprising 40 to 80 mole % of the repeating unit of the formula (10), 29 mole % or less of the repeating unit of the formula (11), 1 to 30 mole % of the repeating unit of the formula (1.2) and 10 to 30 mole % of the repeating unit of the formula (13), ##STR21## wherein R is halogen, C₁ -C₅ alkyl or phenyl; m is an integer of 0 to 2, and when m is 2, the two substituents represented by R may be different from each other.
 6. A heat-resistant aromatic polyester according to claim 1 characterized by comprising 40 to 80 mole % of the repeating unit of the formula (10), 1 to 30 mole % of the repeating unit of the formula (12) and 10 to 30 mole % of the repeating unit of the formula (13), ##STR22##
 7. A method for producing a heat-resistant aromatic polyester which has a resorcinol structure of formula (1) ##STR23## and gives a powder fraction having a lightness (L value) of 80 or more and a red degree (a value) of 3 or less, which powder fraction is obtained by pulverizing the heat-resistant aromatic polyester, sieving the pulverized polyester by Tyler standard sieves and being allowed to pass through 60-mesh sieve but not 325-mesh sieve, which comprises polymerizing a monomer of a resorcinol diacetate produced by reacting a resorcinol having the formula (14) with acetic anhydride in the presence of a tertiary amine, ##STR24## wherein the tertiary amine is present in an amount of 0.02 to 3 pans by weight per 100 parts by weight of resorcinol.
 8. A heat-resistant aromatic polyester resin according to claim 1, wherein the powder fraction has a red degree of 2 or less. 